CN1076433A - The material of forming by carbon compound - Google Patents

The material of forming by carbon compound Download PDF

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Publication number
CN1076433A
CN1076433A CN92114941A CN92114941A CN1076433A CN 1076433 A CN1076433 A CN 1076433A CN 92114941 A CN92114941 A CN 92114941A CN 92114941 A CN92114941 A CN 92114941A CN 1076433 A CN1076433 A CN 1076433A
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China
Prior art keywords
particulate
carbon dust
carbon
content
polymkeric substance
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CN92114941A
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Chinese (zh)
Inventor
K-D·尼克尔
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Citadel Investments Ltd
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Citadel Investments Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B29C48/405—Intermeshing co-rotating screws
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2503/00—Use of resin-bonded materials as filler
    • B29K2503/04—Inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2503/00—Use of resin-bonded materials as filler
    • B29K2503/04—Inorganic materials
    • B29K2503/08—Mineral aggregates, e.g. sand, clay or the like

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Processing Of Solid Wastes (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

The present invention relates to a kind of material of being made up of carbon compound, it can utilize all known plastic processing machineries to be processed into mo(u)lded item, sheet material, tubing or film etc., and have high quality.It can be under the situation of no obvious mass loss repeatedly recycling, particularly have high heating value, can pass through burn processing, can not cause the pollution or of exceeding standard of combustion unit simultaneously by the toxicity objectionable impurities atmosphere pollution that exceeds standard.

Description

The material of forming by carbon compound
The present invention relates to a kind of material of being made up of carbon compound, it can utilize all known plastic processing machineries to be processed into mo(u)lded item, sheet material, tubing or film etc.
On market except obtaining many different types of pure plastics, for example outside polyvinyl chloride, polyethylene (low density and highdensity), polypropylene, polystyrene, the polymeric amide etc., some plastic filler composition is seen from factors such as costs and is had great significance.In order to satisfy the special market requirement, also having some compositions to be mixed in the thermoplastic polymer by the powdered carbon of making particulate, coke powder and refinery coke powdered carbon makes, and in some cases, the filler that the thinnest powder made from coal, coke or petroleum coke can not be taken as on the ordinary meaning has been treated, what have become the necessary component of thermoplastic polymer for they, and the character of this kind plastics is being brought into play decisive influence.
In addition, known also have a kind of method of making the material of plastically deformable, this material is made up of polyethylene and coke fine powder filler, this method adds at least in the polyethylene matrix and to be equivalent to its weight 1/4th, preferably equivalent or more coke fine powder, and be blended together in known manner.(referring to German Patent specification of exhibition 1065607).
Powdered carbon or coke powder do not resemble in the plastic moulding material and can make the character of material become bad the filler of most use, but unexpectedly can improve the physical properties (improving tensile strength, bend tension intensity, unit elongation and cold short stability) of shaped material; Moulding material also is easy to forming process.What be particularly suitable for filling out part polyethylene matrix has bituminous coal coke, petroleum coke and a pitch coke.The polyethylene of particularly low ash content bituminous coal coke and equivalent mixes mutually and can be made into the sheet material with favorable elasticity, and it has filled other fillers in pliability test and in the polyethylene matrix, compare as the material of shale powder, has satisfactory stability is arranged.Shale powder-polyethylene board with same blending ratio is only just accused after the effect of stress in bending several times and is fractureed.
In known method, coke powder is to grind in common mode to form.Produce high-quality moulding material and not only can use high fineness (6400 orders/cm 2), and can use coarsness (900 orders/cm 2) powder.
In the mixture of forming by polyethylene and coke powder, can also add treating compound, lubricant and other known additive, for example ultra-violet stabilizer, thermo-stabilizer etc.
Should be pointed out that especially the mo(u)lded item made from known moulding material has good weldability.
Also has the known moulding material of a class, make and contain diameter by polyethylene, polypropylene, polybutene, ethylene-propylene, ethene-butylene or propene-1-butene copolymer less than 60 microns particulate coke, contain 200 to 400 parts of particulate petroleum cokes in 100 parts of polymkeric substance wherein, wherein have 80% mean particle size between 0.75 to 50 micron (referring to No. the 1259095th, German Patent specification of exhibition) at least.The mechanism of this moulding material is that the size-grade distribution of petroleum coke particulate can influence the realization of final product high structural strength.In fact can not in this polymkeric substance, add 150 to 200 parts of mean diameters greater than 50 microns (! ) the petroleum coke particulate.This in addition product does not have desired high tensile impact intensity and bend tension intensity yet.If, then can unexpectedly reach the most favourable physical properties with the further refinement of petroleum coke and with the particulate and the mixed with polymers of granularity between 0.75 to about 50 microns.
In order to make this known moulding material, can adopt any commercially available common polyolefine or mix polyolefine, its fusing coefficient is between 10 to 0.2, and molecular weight is between 50000 to 700000.
Before petroleum coke being used in the known moulding material, will pass through the grinding of ball mill, rod mill, hammer mill pulverizes petroleum coke and calibration, perhaps the winding-up by steam or air is thrown to coke granule on the surface, by spinner blade (Perlman [Pallmann]. fuel pulverizing plant) centrifugation, by ultrasonic vibration or use spacing petroleum coke to be pulverized and calibration as 0.0254cm or the littler steel rider that is oppositely arranged.
Because petroleum coke, particularly the hardness of high relatively ash content petroleum coke may be quite high, for example be 7.5-8 this (Mohs) scale that rubs, so when pulverizing petroleum coke with aforesaid method, shredding unit can wear and tear soon, and cause scrap metal, iron filings or steel cuttings to be sneaked into by in the abrasive, its consequence or must be arduously and of a high pricely it is separated perhaps causes the character of moulding material not accepted by all Application Areass.
Also have a kind of known method to be used to make special grinding coal in addition, with filler as plastics, it is with hard coal, place nonoxidizing atmosphere to pulverize as hard coal, be not more than 2.5 microns until averageparticle, and will reach size-grade distribution especially is, at least 90% material particle size is less than 5 microns (referring to No. the 1592914th, German Patent prospectus).
This known coal dust generally obtains by pulverizing or grind common coal, preferably obtains by autogenous mill, particularly adopts the shredder that utilizes fluid operating that generally is referred to as " Cyclone mill ".This class shredder must not contain air or oxygen free gas when pulverizing, because otherwise fluid will produce adverse influence to polished coal, the coal dust of being processed for example can be used for rubber and other polymkeric substance.In known coal ground, it was necessary keeping nonoxidizing atmosphere, because coke fines can form very high reactivity when pulverizing; This is likely that fracture owing to key causes.This phenomenon can occur in process of lapping, and its consequence is that the key of fracture and airborne oxygen react, thereby have lost its reactivity.If yet to the in addition enough protections of the key of fracture, just this key can with other composition phase reactions of polymkeric substance, thereby form polymkeric substance or rubber with outstanding physical properties.
The influence of oxygen can stop by certain inert gas atmosphere in crushing process, when classification, then can spray 0.1 to 1% the Zinic stearas be equivalent to its weight approximately to product, each particulate is all covered, until obtaining consistent relatively coating by Zinic stearas.When protected coke powder was added in the natural rubber and cures, coating was promptly fusible.
Not only can be used as the filler of natural rubber with the coal powder of known method preparation, but also can be as the packing material of common plastics.
The method that also has a kind of known manufacturing coke mixture as described in No. the 1719517th, German Patent prospectus, can make the particulate of grinding have very high surface-area amplification degree, and it is applicable to and is blended in the plastics.When utilization is mixed method or injection moulding and is made plastics tubing, plate, sheet and other mo(u)lded items, can in plastics, clamp-on the raw material of wood-charcoal material of conduction, make it possess electronics antistatic property (seeing the German Patent prospectus No. 2017410), and for the modified plastics that contains lipophilicity graphite, natural or synthetic graphite secluding air in organic liquid are ground and make Graphite Powder 99.
The shortcoming of all these materials is, the complicated process of preparation of coal or coke, and the cost height, thus improved the price of the unit weight of finished product, although these materials have lot of advantages, because price former thereby left alone without help stayed very little use range.
In addition, the ability of the regeneration of this plastics or plastics-fill composition is also low more or less excessively.Its quality of known up to now plastic filler-plastics composite regeneration back has very big decline, continues to use so often regenerated plastics and new plastic will be combined, and does not perhaps mix with the latter and makes the mo(u)lded item of low value.
In addition the problem that also can produce is, this material will spend very big cost to remove, and particularly disposes, if can dispose.This material for example can not decompose in the refuse tip voluntarily, and will produce objectionable impurities when burning in waste gas.Because the usage quantity of plastics constantly increases, it is particularly serious that this shortcoming just seems.For example only in nineteen ninety in Germany, each state of the German east that not very increases newly, fluidization is learned fiber and has been produced the plastics more than 9,000,000 tons altogether interior.The rate of increase in plastics market every year 8% of determining according to official will consume nearly 19,000,000 tons plastics during by 2000 every year in the territorial limits of former federal republic of germany.This problem becomes can't finishing of task when only just can make such as the packing set quota to 1996 of government promulgation year, because the processing of the old Plastic wastes that produce in industry and the family is insurmountable at present, its coefficient of recovery only has an appointment 7% at present in West Germany.Yet the rate of recovery of aluminium is 38.3%, and waste paper is 40.7%, and cullet is 43.2%.If just can not bank up simply by biolytic plastics, the stores that then accumulates will enter unforeseen destiny in the long term, the diffusion that will be converted by the material in empty G﹠W of its consequence.
The burning of most of plastics, for example the burning in the incineration firing device also can be owing to the toxicity connection oxine or other materials that install the mass filler ash content that is produced and produce in smoke evacuation owing to burning cause serious environmental burden.This class toxicity risk material group can discharge through 250 ℃ to 400 ℃ temperature range the time in burning, and enters atmosphere near the face of land through smoke evacuation.Cause is in fearing to occur this type of problem, so allow to set up the special-purpose incineration firing device that is used for extraordinary rubbish at present hardly on policy.
The work of very expensive at first is that Plastic Packaging Materials and household garbage are put into different categories by its kind, for example tells ballpoint pen, film, container, barrel cage, toy and man-made fiber from the household garbage that mixes.All these plastics are by new plastic or secondary plastics, and promptly the plastics crossed once of reclaiming are formed at least.The secondary plastics are compared its quality and are become bad greatly owing to heat effect and radiation effect and fusing in removal process and granulation again with new plastic.If carry out not thoroughly owing to put into different categories, plastics variety impure (polyethylene, polypropylene, polystyrene, polycarbonate, polyester, polymeric amide etc.) or plastics and secondary plastics are mixed to be reclaimed, perhaps containing in the plastics at first is pigment, stablizer, softening agent or other additives that mixes in its first Application, then can make quality further become bad, so that cause from the reason of economy and forbid utilizing again these class plastics.So have only seldom a part of depleted plastics can obtain reclaiming.Plastic quality does not have the bad recovery of obvious change and can only appear in the simple plastics of kind.But nonetheless, also will in the single variety plastics, classify by filler or the pigment by its use, so mass loss is inevitable.
Even if under support, also be difficult in the purer kind of 8-10% (as polyethylene) and the similar kind of 10-13% and about 10% bulk variety and the impurity collected in the future in whole plastic prods such as " dual system " set up in Germany.
The regenerated plastics since its quality must descend, the defective of its outward appearance with and extravagent price and can not being accepted by market inevitably.According to present law standard and DIN(Deutsche Industry Norm) regulation, the use of reprocessed plastic(s) is very limited.
Can think that in sum the recovery of plastics is because the cost of its collections, classification, processing again, granulation, transportation and the cost of sale is very high again, so be limited on seldom the quantity.
The maker or seller of broken in addition plastic waste product has improved 25-30% because of it reclaims obligation with the market value of its plastic prod, with compensation owing to collect and classification and in addition because of handling a large amount of expenditures that these plastics are paid.
Plastic reclaimed method up to now can make old reprocessed plastic(s) be piled into the mountain sooner or later, and they no longer can be regenerated, and also no longer can be used for burning.
The task of the present invention's proposition is for this reason, make a kind ofly can cheap produce, almost available all existing plastic processing machinery and device processing, the material of forming by carbon compound, it is compared with the known material of being made up of carbon compound, not only should possess same at least good machinery, physics and process industrial art performance, and it is in addition can also under the condition that does not produce mass loss, recycle again, and processed under the situation of compliance with environmental protection requirements without a doubt.
This task is found and can solves in simple mode, its scheme is, by low harmful substance content and low ash content bituminous coal is arranged except containing in this carbon compound with very high stroke speed, outside the particulate carbon dust that coke or petroleum coke are made, the thermoplastic polymer that also contains hydro carbons, this polymkeric substance is with the carbon dust particulate, by the carbon dust particulate in the closed system of materials processing device because of pulverized the bond energy that discharges by high-speed impact, do not produce the material of mass loss without other additives promptly are combined to a kind of can repeatedly the recycling, the calorific value of this material is greater than 37500 kilojoule per kilogram.
Utilize the present invention can be implemented in and utilize solid fuel, as be coke, coal, bituminous coal, petroleum coke, the particularly heat energy of the carbon of hard coal form (burning) before, can use it for multiple novel earlier, different purposes, but prerequisite is that the harmful substance contents and the ash oontent of this fuel is low, and is processed into microgranular carbon dust with very high stroke speed.The contriver finds that the particulate of this carbon dust discharges bond energy because of being pulverized by high-speed impact in the closed system of materials processing device, under the effect of this energy, just can be combined to described material with thermoplastic polymer without other additives.This material and by the physics of the product of its manufacturing and processing performance and at present employed any polymer phase than all having greatly improved.Beat allly be, this type material can repeatedly be recycled and mass loss not occur, and can change heat energy into by burning by high heating value at last, simultaneously in the combustion chamber or the objectionable impurities in the flue gas that produces of burning but can not exceed permissible value.Thisly be in the type material in the circulation thereby be a kind of energy reserves that helps environment protection.
Because the present invention has been arranged, this energy reserves thermotropism conversion of energy also can carried out after repeatedly recycling, thereby more helps environmental protection, neither increases cost, does not also need place where the garage is piled up or incineration firing device.
The pulverizing of this fuel can be carried out in being suitable for carrying out the shredding unit that high-speed impact type pulverizes in principle.But it is found that the most favourable and cheap and economic especially pulverizing is to use as 3802260D2 number described eddy current type pulverizer of German Patent.This eddy current type pulverizer with in relative rotation, radially stacked blade ring work, make to form the vortex cavity in the annular chamber between the blade ring fuel pellet bump mutually at full speed in this vortex cavity, thereby the deleterious galling of unlikely generation.Average each fuel particles when it passes the vortex cavity that radially stacks together will with other particle collisions eight times, particularly in last vortex cavity between penult vortex cavity and siphonal lobe loop and outside the opposite side of blade ring can produce the stroke speed that approaches the velocity of sound.
Time of an eddy current type crusher for crushing with compare very of short duration at a table grinder or such as the fuel pulverizing time in other shredding units, it only is 0.5 second, can accomplish that so not only tooling cost is lower than other shredders, but also can realize a technologic significant advantage, because the bond energy that is discharged (mainly being ion or electronics) can be not soon is imported into the earth through the hardware of processing unit (plant).
The material that carries out in the eddy current type pulverizer of the above-mentioned type is pulverized and is compared with other grinding modes, also has another important advantage.Because the stroke speed height in pulverizing, particularly allowing fuel particles oneself collide mutually, is not by centrifugal force particulate to be thrown on the wall or on the analogue, makes the surface-area compression by the ball in the ball mill fully, thereby can allow very high bond energy discharge, and keep major part wherein.When this bond energy mixes with the hydrocarbon polymer of polymkeric substance in fuel particles, almost all be used to improve the quality of material of the present invention in forcing machine.In above-mentioned high-speed impact type crushing process, what at first discharge is the most weak bond energy, and this is diverse (for example No. the 1592914th, the German Patent prospectus) with the situation of shearing or tearing pulverizing.In described high-speed impact type crushing process, the most weak bond energy of the fuel particles always that discharges is so fuel can be decomposed into more stable particulate.The product that is generated can be described as micro mist, has the fixed bond quality in its particulate and enters in the chemical compound of corresponding polymer, thereby bring outstanding performance for described type material.
The high-speed impact type pulverizing can be hydrogen ion/electronics and carbon-electronics provides excitation energy, makes its energy freedom of entry orbit or enters higher energy level.This process is relevant with temperature.So high-speed impact type pulverizing of the present invention and activated carbon powder and the mixing of polymkeric substance in forcing machine can be carried out under the condition that adds heat, and partly in inert atmosphere, carry out, react with bond energy and the airborne oxygen of avoiding discharging.Import the reactive adaptation that heat energy can also improve carbon dust among reaching before this external forcing machine.The contriver finds that carbon dust and polymkeric substance are combined into the optimum operating temperature of described material between 240 ℃ to 300 ℃ in forcing machine.If too reduce this temperature, then just can not make this type material possess high value material property, comprise good specific conductivity.
The above-mentioned course of processing of pulverizing near the high-speed impact type of the velocity of sound can make anthracitic surface change, form diameter less than 3.6 microns micropore on fine particle tissue, its effect is that the surface area ratio ball mill or the mach hard coal of vibration of particulate increased 10 times.It is 28m that (granularity is 40 microns layerings) high-speed impact type is pulverized the surface-area that can reach 2/ g, and ball mill or vibrating ball mill has only 2.6m 2/ g and 2.8m 2/ g.The method that micropore produces is that in the high-speed impact crushing process near the velocity of sound, the temperature of knockout process is raised to 300 ℃ in short time, and the volatile component in the hard coal is discharged.Be noted that especially these micropores can increase anthracitic water absorbability (can absorb and reach 6% moisture, even absorb a part from ambient air).The reason that this ability in the micropore that liquid is sucked and remains on produces is the molecular structure of corresponding liquid.H +Ion perhaps is H at least +Idol level can occupy corresponding position in micropore, thereby makes OH -Ion or OH -Dipole no longer can take up position.(this process and time correlation) then will correspondingly reduce it and accept band OH if continuing to prolong its storage period before the processing hard coal with forcing machine -The ability of group molecule.This process plays an important role when particularly pulverized anthracite and polymkeric substance mix in forcing machine with carbon dust, therefore must pay special attention to.
From the affine H of size degradation hard coal +This phenomenon that can be confirmed by the absorbent test with water or phenol of ion is set out, can reason out, and in material of the present invention, polymkeric substance CH - 2CH 2Chemical combination has been together for hydrogen in the chain and the carbochain C-C-C-in the hard coal.
As polymkeric substance of the present invention should be pure polyethylene or polypropylene as far as possible, and they for example can melt in the rotary extruding at double-screw type and screw rod under 240 ℃ to 300 ℃ temperature in the same way.In melt, add manufactured size degradation particulate hard coal carbon dust continuously, preferably under 200 ℃ to 300 ℃ temperature, add.Anthracitic content can change between 40-80M% according to the difference of particle type.The extrudate of being produced is carried out granulation again, so that under the condition that does not reduce quality, it can be stored, and then be processed into the required product in market (for example moulding compound, sheet material, tubing with the known plastic processing machinery of almost all kinds or device, film and the container of making because of its chemical property and resistance to ultraviolet(ray) radiation matter, storage tank, barrel cage etc. are to be used to handle chemical waste and production of hybrid seeds rubbish).
Be suitable for being processed into the most handy low ash content of carbon dust of particulate and low-sulfur hard coal as raw material, its analytical value is as follows:
Carbon content is greater than 94%
Ash oontent is less than 3.5%
Sulphur content is less than 1.5%
Volatile content is less than 2.5%
Calorific value is greater than 35500KJ/Kg
This material is that 70% Powdered hard coal and 30% polyethylene are formed by weight percent.
According to the present invention, the pulverized anthracite that is processed into particulate and polyethylene be chemical combination mutually, forms a kind of novel material, and it is compared with pure polyethylene has following performance number:
Characteristic value DIN(Deutsche Industry Norm) polyethylene type material (standard type)
Tensile strength 53455 25N/mm 235N/mm 2
Unit elongation 53,455 6% 2%
Flexural strength 53452 18N/mm 244N/mm 2
Young's modulus 53457 840N/mm 22460N/mm 2
Impelling strength 53453 non-cracking non-crackings
78 ℃ 107 ℃ of softening temperature ISO306 VICAT
Specific conductivity 2 * 10 14 Ω 1 * 10 5Ω
Cold shock toughness non-cracking non-cracking
Other data and relatively see attached list shown in.
Above performance number is better than great majority by the known material of prior art.This type material is compared with pure polyethylene under the atmospheric condition effect, and its tensile strength descends also seldom.Even if impelling strength still can remain unchanged after 500 hours.
Particulate carbon dust of the present invention, but according to the difference size degradation of the use of material regulation with to sieve into granularity be powder between 10 microns to 90 microns.Its weight share in type material is between 20 to 70%, and remaining is a polymkeric substance, and both form 100% weight jointly.
Significantly, the calorific value of this type material has surpassed common fuel, and is as shown in the table:
The material calorific value
Bituminous coal 21-33KJ/g
Sweet natural gas 37KJ/g
Type material reaches 38.5KJ/g(according to the polymer content difference)
Therefore this type material can reclaim its heat energy through repeatedly recycling the back by the burning in power plant, cement mill, Lime Factory etc. or incineration firing device without a doubt, thereby helps environment.The burning plastics will be paid the expense that reaches 400 mark/tons in the incineration firing device of special use up to now.If yet provide high performance fuel will pay to the supplier on the contrary to power plant, cement mill, Lime Factory etc.! Because the carbon content in this material surpasses 90%, so its waste material also can be used to improve the quality of steel by Iron And Steel Industry! And yet can not produce pollution or make the objectionable impurities in the smoke evacuation exceed emission standard in the burning combustion unit.
If material be placed on the isolated fully system of processing of outside air in process at inert gas atmosphere or in inert gas atmosphere and atmosphere less than 3% remaining oxygen content; and before continuation processing, keep hermetically sealed packaging with isolate from outer air always; then this material granule or powder just can possess outstanding processing quality, have high strength, high temperature stability and high specific conductivity.
As for make the few processing of harmful substance contents then can be by making the heating plastic plastics additive, stablizer, electric conductor or the pigment that only contain selection realize, make and wherein do not contain the material that toxic action takes place in the incendiary flue gas of material or its product, perhaps do not make objectionable impurities exceed the permission emission standard.
The contriver finds that the Powdered hard coal in this material accounts for 70% of gross weight, and polyethylene accounted for 30% o'clock, and this material can not be subjected to the erosion of chemical reagent and can tolerate ultraviolet radiation under 37 ℃ the envrionment temperature being up to.(test period is 2000 hours, is limited to 60 microns on the granularity of pulverized anthracite).
Utilize a kind of electronics accelerator material of the present invention to be soaked into the intensity and the thermal load (for example tubing, container, jar, mo(u)lded item etc.) that can also improve greatly by its products made thereby.Certainly its thermoplasticity also can be parallel to the degree of infiltration and lower.The material that the degree of depth is soaked into no longer is suitable for recycling, but its can not lose as having high heating value and harmful substance contents significant advantage low and that help the fuel of environmental protection treatment!
Contrast accompanying drawing below and consider that parameters illustrates the main character of this type material.
As shown in Figure 1, material of the present invention granularity be 60 microns anthracitic content when improving its tensile strength (=extension limit stress) also increase.Basis relatively is 100% pure polyethylene (PE).Anthracitic analytical value characteristic as claimed in claim 2 is described.When the particle size reduction of hard coal powder, tensile strength has only very little raising.
Shown in Figure 2 is the increase of this type material intensity and the relation between the hard coal quality share.Basis relatively is that intensity is 25.2N/mm 2Polyethylene and intensity be 32.6N/mm 2Polypropylene.Anthracitic granularity is 60 μ.What is interesting is, be higher than significantly with the material of polypropylene as polymeric constituent with the tensile strength of polyethylene as the material of polymeric components.Obviously the hard coal that processes by the present invention is more stable than polypropylene with poly reaction.Along with the increase of hard coal quality share, the growth of the intensity of two kinds of materials is different.
Relation in the impelling strength of shown in Figure 3 is type material and the material between the different hard coal granularity.When the granularity of hard coal powder is 90 microns, the quality share reaches at 30% o'clock, and impelling strength remains unchanged basically fully.Along with the increase of hard coal quality share, impelling strength just descends, when hard coal quality share is 60% to reach its lower value 20%.When the granularity of hard coal powder was respectively 60 microns, 30 microns and 10 microns, material also presented similar character.Higher and wish to impact when tough also high when the hard coal quality share of this novel material, less granularity is selected in suggestion.
As shown in Figure 4, the impelling strength of material of the present invention can not change because of the influence of atmospheric condition.Polyethylene then became fragile after 250 hours.In industrial production, poly this shortcoming is eliminated by adding stablizer usually, and material of the present invention does not then need to use this additive.
As shown in Figure 5, anthracitic quality share also can influence specific conductivity.Specific conductivity reaches maximum value (being equivalent to the surface resistivity minimum) when anthracitic quality share is 60%.
As shown in Figure 6, the tensile strength of material virtually completely maintains the original state after repeatedly recycling.Unit elongation then increases to some extent.Just impelling strength has just descended 50% after reclaiming for the third time.Increase along with reclaiming round-robin, notch shock toughness descends thereupon.Even if but these two indexs remain fully enough reclaim circulation through five times for many products after.Softening temperature has only a little decline.Reclaiming cycle index can't influence the high heating value of this novel material.
As shown in Figure 7, hard coal quality share also can influence the softening temperature of this type material.Pure poly softening temperature is 78 ℃, and as 100% starting point, the softening temperature that then has the material of 70% hard coal quality share is to be almost 137%, promptly about 107 ℃ under 60 microns the condition in granularity with it.

Claims (11)

1, form by carbon compound, can utilize all known plastic processing machineries to be processed into mo(u)lded item, sheet material, tubing, the material of film etc., it is characterized in that, in the described carbon compound except containing with very high stroke speed by low harmful substance content and low-ash size degradation bituminous coal, outside the particulate carbon dust that coke or petroleum coke are made, the thermoplastic polymer that also contains hydro carbons, this polymkeric substance is with the carbon dust particulate, by carbon dust particulate bond energy because of being discharged in the closed system of materials processing device by high-speed impact, without other additives is that chemical combination becomes a kind of can repeatedly the recycling and do not produce the material of mass loss, and the calorific value of this material is greater than 37500KJ/Kg.
2, material as claimed in claim 1 is characterized in that, preferably adopts low ash content and low-sulfur hard coal as the carbon dust that is processed to particulate, and its analytical value is as follows:
Carbon content＞94%
Ash oontent＜2%
Volatile content＜2.5%
Sulphur content＜1.5%.
As material as described in claim 1 and 2, it is characterized in that 3, the particulate powdered carbon is ground into granularity between 10 μ m and the 90 μ m by the service requirements of material, and makes it account for 20 to 70% of material gross weight, all the other are polymkeric substance.
4, as claim 1 and 3 described materials, it is characterized in that thermoplastic polymer preferably adopts polyethylene or polypropylene.
5, as claim 1 and 4 described materials, it is characterized in that, carbon dust be preferably in the eddy current type disintegrator with up to the high stroke speed of 320 meter per seconds by size degradation, and have low galling amount.
6, as the described material of claim 1 to 5, it is characterized in that, described material be placed in the isolated fully system of processing of outside air in inert gas atmosphere or in inert gas atmosphere and atmosphere, process and storage in the air hermetic packing that continues always to remain on before processed with isolate from outer air less than 3% remaining oxygen content.
As the described material of claim 1 to 6, it is characterized in that 7, the chemical combination between particulate size degradation carbon dust and the selected polymkeric substance carries out in forcing machine, and make processing temperature between 200 ℃ to 300 ℃ by the input heat.
8, as the described material of claim 1 to 7, it is characterized in that, be added to interior particulate size degradation carbon dust of forcing machine and selected polymkeric substance at 200N/mm 2Operating pressure under mixed and processing.
As the described material of claim 1 to 8, it is characterized in that 9, particulate size degradation carbon dust was heated to working temperature earlier before being added to forcing machine.
10, as the described material of claim 1 to 9, it is characterized in that, only contain in the additive in the thermoplastic polymer of interpolation, stablizer, electric conductor or the pigment and do not cause in material or its product incendiary flue gas toxigenous material or do not cause objectionable impurities to exceed the permission emission standard.
As the described material of claim 1 to 10, it is characterized in that 11, this material is that 60% Powdered hard coal and 40% polyethylene are formed by weight percent preferably.
CN92114941A 1991-12-04 1992-12-04 The material of forming by carbon compound Pending CN1076433A (en)

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DEP4140025.9 1991-12-04
DE4140025A DE4140025C2 (en) 1991-12-04 1991-12-04 Material consisting of carbon compounds

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FI (1) FI933456A0 (en)
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DE10152189B4 (en) * 2001-10-23 2006-03-23 Hubert Rosing Process for the production of semi-finished products from ultra-high molecular weight polyethylene with anthracite, semifinished products thus produced and their use
RU2491302C2 (en) * 2008-10-13 2013-08-27 Закрытое акционерное общество "Макполимер" Electro-conductive composite material based on polypropylene and globular carbon nano-filler
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US3404120A (en) * 1965-08-02 1968-10-01 Marathon Oil Co Polymer compositions containing coal which has been ground in a non-oxidizing atmosphre
US3846523A (en) * 1967-12-12 1974-11-05 American Mfg Co Inc Method of forming expanded composite materials in the absence of recognized blowing agents
DE2017410A1 (en) * 1970-04-11 1971-10-28 Conradty Fa C Plastic for the production of pipes, plates, discs and other shaped bodies by extrusion and injection molding
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